Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • E—FIXED CONSTRUCTIONS
  • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
  • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
  • E01C7/00—Coherent pavings made in situ
  • E01C7/08—Coherent pavings made in situ made of road-metal and binders
  • E01C7/18—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2555/00—Characteristics of bituminous mixtures
  • C08L2555/20—Mixtures of bitumen and aggregate defined by their production temperatures, e.g. production of asphalt for road or pavement applications
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2555/00—Characteristics of bituminous mixtures
  • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
  • C08L2555/80—Macromolecular constituents
  • C08L2555/84—Polymers comprising styrene, e.g., polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers

Definitions

• the present invention relates to an asphalt composition.
• asphalt compositions are widely used for road pavement, sound insulation sheets, asphalt roofing and the like.
• Various polymers are added to such an asphalt composition in order to add performance according to the application.
• ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, rubber latex, block copolymer composed of conjugated diene and vinyl aromatic hydrocarbon, and the like are added.
• Patent Document 1 For example, a technique is disclosed in which sulfur is used (see, for example, Patent Document 1), and sulfur and a vulcanizing agent, and further a sulfur-containing vulcanization accelerator is used in combination (for example, see Patent Document 2).
• composition disclosed in Patent Document 3 has a problem that the softening point and the high temperature storage stability property balance are insufficient and the elongation is inferior.
• composition disclosed in Patent Document 4 uses a block copolymer composed of a normal vinyl aromatic hydrocarbon and a conjugated diene, the high-temperature storage stability is insufficient. There is a problem that it cannot be used as a single asphalt waterproof sheet.
• composition disclosed in Patent Document 5 has a high vinyl aromatic compound content, it has excellent high-temperature storage stability, but sufficient properties in softening point and elongation cannot be obtained. It cannot be used as a problem.
• asphalt is known to have different ratios of the four components A: saturated, B: asphaltene, C: resin, and D: aromatic depending on the crude oil production area and refinery.
• A saturated
• B asphaltene
• C resin
• D aromatic depending on the crude oil production area and refinery.
• the difference in these components greatly affects the physical properties of the asphalt composition, the softening point is low, the high-temperature storage stability that can be judged from the change in softening point after high-temperature storage is insufficient, and There is a problem that digging and solubility are poor.
• the present invention has been made in view of the above problems, and provides an asphalt composition having a high softening point, high elongation, low melt viscosity, and excellent rutting resistance and high-temperature storage stability. Objective.
• the present inventors have found that the above problems can be solved if the composition is composed of a block copolymer having a specific structure and asphalt having a specific composition, The present invention has been completed.
• the present invention is as follows. [1] 0.5 to 20 parts by mass of a block copolymer, 100 parts by weight of asphalt,
• the block copolymer comprises a polymer block (A) mainly comprising a vinyl aromatic monomer unit, and a copolymer block (B) comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit.
• the content of the vinyl aromatic monomer unit in the block copolymer is 20% by mass or more and 60% by mass or less
• the content of the polymer block (A) in the block copolymer is 10% by mass or more and 40% by mass or less
• the hydrogenation rate of double bonds in the conjugated diene monomer unit of the block copolymer is 40% or more and 100% or less
• the colloidal index of the asphalt ((saturated content + asphaltened content) / (resin content + aromatic content)) is 0.30 or more and 0.54 or less, and the saturated content. Is 11 mass% or less, Asphalt composition.
• the block copolymer has a loss tangent peak top in a range of ⁇ 70 ° C. or more and 0 ° C.
• the hydrogenation rate of a double bond in the conjugated diene monomer unit of the block copolymer is 50% or more and 90% or less, according to any one of the above items [1] to [4].
• Asphalt composition. [6] The asphalt according to any one of [1] to [5], wherein a hydrogenation rate of a double bond in the conjugated diene monomer unit of the block copolymer is 60% or more and 90% or less.
• Composition [7]
• the conjugated diene monomer unit of the block copolymer is derived from a conjugated diene monomer unit (a) derived from a 1,2-bond and / or a 3,4-bond and a 1,4-bond.
• a conjugated diene monomer unit (b) When the total content of the conjugated diene monomer unit is 100% by mass, The content of the alkenyl monomer unit (a1) hydrogenated with the conjugated diene monomer unit (a) is 10% by mass or more and 50% by mass or less, The content of the alkenyl monomer unit (b1) in which the conjugated diene monomer unit (b) is hydrogenated is 0% by mass or more and 80% by mass or less, The sum of the contents of the conjugated diene monomer unit (a2) not hydrogenated after hydrogenation and the conjugated diene monomer unit (b2) not hydrogenated after hydrogenation is 0% by mass or more and 90% by mass or less.
• the content of the conjugated diene monomer unit (a) derived from 1,2-bond and / or 3,4-bond is relative to the total content of the conjugated diene monomer unit of the block copolymer.
• the asphalt composition according to any one of [1] to [10], wherein the penetration of the asphalt is more than 60 and 80 or less.
• an asphalt composition having a high softening point, high elongation, low melt viscosity, excellent rutting resistance and high-temperature storage stability can be provided.
• the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
• the present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.
• Asphalt composition of this embodiment 0.5 to 20 parts by mass of a block copolymer, 100 parts by weight of asphalt,
• the block copolymer comprises a polymer block (A) mainly comprising a vinyl aromatic monomer unit, and a copolymer block (B) comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit.
• the content of the vinyl aromatic monomer unit in the block copolymer is 20% by mass or more and 60% by mass or less,
• the content of the polymer block (A) in the block copolymer is 10% by mass or more and 40% by mass or less,
• the hydrogenation rate of double bonds in the conjugated diene monomer unit of the block copolymer is 40% or more and 100% or less;
• the colloidal index of the asphalt ((saturated content + asphaltened content) / (resin content + aromatic content)) is 0.30 or more and 0.54 or less, and the saturated content. Is 11 mass% or less.
• the block copolymer of this embodiment includes a polymer block (A) mainly composed of a vinyl aromatic monomer unit, and a copolymer block containing a conjugated diene monomer unit and a vinyl aromatic monomer unit ( B), the content of the vinyl aromatic monomer unit is 20% by mass or more and 60% by mass or less, and the content of the polymer block (A) is 10% by mass or more and 40% by mass or less. And the hydrogenation rate of the double bonds in the conjugated diene monomer unit is 40% or more and 100% or less.
• the “conjugated diene monomer unit” is a unit per conjugated diene compound generated as a result of polymerization of the conjugated diene compound.
• the conjugated diene monomer unit is referred to as a “conjugated diene monomer unit” regardless of before and after hydrogenation.
• the conjugated diene compound is a diolefin having a pair of conjugated double bonds.
• the conjugated diene compound is not particularly limited.
• 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene examples include 2-methyl-1,3-pentadiene and 1,3-hexadiene. Of these, 1,3-butadiene and isoprene are preferred.
• Two or more conjugated diene compounds may be used.
• the “vinyl aromatic monomer unit” is a unit per vinyl aromatic compound generated as a result of polymerization of the vinyl aromatic compound.
• the vinyl aromatic compound is not particularly limited.
• the vinyl aromatic compound may be used alone or in combination of two or more.
• the polymer block (A) is a block mainly composed of vinyl aromatic monomer units.
• “mainly” means that the polymer block (A) contains a vinyl aromatic monomer unit in an amount of more than 95% by mass and 100% by mass or less, preferably 96% by mass to 100%. It means that it is contained by mass% or less, and more preferably it is 97 mass% or more and 100 mass% or less.
• the content of the polymer block (A) is 10% by mass or more and 40% by mass or less, preferably 13% by mass or more and 35% by mass or less, and more preferably 20% by mass with respect to the entire block copolymer. It is 30 mass% or less, More preferably, it is 17 mass% or more and 22 mass% or less. When the content of the polymer block (A) in the polymer is within the above range, the softening point and high-temperature storage stability are further improved.
• the content of the polymer block (A) in the polymer when the polymer is hydrogenated is substantially equal to the content of the polymer block (A) before hydrogenation with respect to the polymer.
• the content of the polymer block (A) in the polymer when the polymer is hydrogenated may be obtained as the content of the polymer block (A) before hydrogenation.
• the copolymer block (B) is a block containing a conjugated diene monomer unit and a vinyl aromatic monomer unit, and preferably the vinyl aromatic monomer unit content is 5 mass. % Or more and 95% by mass or less.
• the content of the vinyl aromatic monomer unit in the copolymer block (B) is preferably 5 from the viewpoint of the softening point and rutting resistance (G * / sin ⁇ ) of the asphalt composition. It is at least mass%, more preferably at least 20 mass%, even more preferably at least 25 mass%.
• the content of the vinyl aromatic monomer unit in the copolymer block (B) is preferably 95% by mass or less, more preferably from the viewpoint of high-temperature storage stability and elongation of the asphalt composition. It is 50 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 30 mass% or less.
• the rutting resistance is usually determined by the dynamic stability (DS value) obtained by a wheel tracking test for a composition containing aggregate similar to that of actual road pavement.
• DS value dynamic stability
• the value of G * / sin ⁇ which is an index of dynamic stability described in the examples described later, can be measured to determine rutting resistance.
• the copolymer block (B) is preferably a random block.
• “random” means a state in which the number of continuous vinyl aromatic monomer units in the block copolymer is 10 or less.
• the content of the copolymer block (B) is preferably 60% by mass or more and 90% by mass or less, more preferably 65% by mass or more and 85% by mass or less, and further preferably, with respect to the block copolymer. It is 70 mass% or more and 80 mass% or less.
• the solubility and softening point of the block copolymer in the asphalt composition tend to be further improved.
• the content of the polymer moiety of the short chain vinyl aromatic monomer in the copolymer block (B) is 100% by mass of the vinyl aromatic monomer unit in the polymer block (B). On the other hand, it is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and still more preferably 90% by mass or more.
• the upper limit of the content of the short chain vinyl aromatic monomer polymerization portion in the copolymer block (B) is not particularly limited, but is preferably 100% by mass or less, more preferably 99% by mass or less. is there.
• the content of the polymer moiety of the short chain vinyl aromatic monomer in the polymer block (B) is within the above range, the compatibility between the block copolymer and asphalt, elongation, and high-temperature storage stability are further improved. It tends to improve.
• the “short chain vinyl aromatic monomer polymerization portion” is a component composed of 2 to 6 vinyl aromatic monomer units in the polymer block (B).
• the content of the short-chain vinyl aromatic monomer polymerization portion was such that the content of the vinyl aromatic monomer unit in the polymer block (B) was 100% by mass, and 2 to 6 of them were connected. It is calculated
• the content of the two connected vinyl aromatic monomer units is preferably 10% by mass or more and 45% with respect to 100% by mass of the vinyl aromatic monomer unit content in the polymer block (B). It is not more than mass%, more preferably not less than 13 mass% and not more than 42 mass%, and still more preferably not less than 19 mass% and not more than 36 mass%.
• the content of the two linked vinyl aromatic monomer units is within the above range, the compatibility between the block copolymer and asphalt, the elongation, and the high-temperature storage stability tend to be further improved.
• the content of the three connected vinyl aromatic monomer units is preferably 45% by mass or more and 80% by mass with respect to 100% by mass of the vinyl aromatic monomer unit content in the polymer block (B). It is not more than mass%, more preferably not less than 45 mass% and not more than 75 mass%, and still more preferably not less than 45 mass% and not more than 65 mass%.
• the content of the three linked vinyl aromatic monomer units is within the above range, the compatibility between the block copolymer and asphalt, the elongation, and the high-temperature storage stability tend to be further improved.
• the content of the vinyl aromatic monomer unit is 20% by mass or more and 60% by mass or less, preferably 33% by mass or more and 55% by mass or less with respect to the block copolymer. Preferably they are 37 mass% or more and 48 mass% or less, More preferably, they are 40 mass% or more and 45 mass% or less.
• content of the vinyl aromatic monomer unit in the block copolymer is within the above range, the softening point, the elongation, and the balance between the softening point and the elongation of the asphalt composition are further improved.
• content of a vinyl aromatic monomer unit can be measured by the method as described in the Example mentioned later.
• the content of vinyl aromatic monomer units in the block copolymer is the content of vinyl aromatic monomer units in the block copolymer before hydrogenation. Since they are approximately equal, the content of the vinyl aromatic monomer unit when the block copolymer is hydrogenated may be obtained as the content of the vinyl aromatic monomer unit before hydrogenation.
• the hydrogenation rate (mol%) which is the content of hydrogenated conjugated diene monomer units in the total content of conjugated diene monomer units, ie, in the conjugated diene monomer units.
• the hydrogenation rate of the double bond is 40% or more and 100% or less, preferably 40% or more and 95% or less, more preferably 50% or more and 90% or less, and more preferably 60% or more and 90% or less. It is as follows.
• the hydrogenation rate in the block copolymer is in the above range, the compatibility with asphalt is excellent, and the performance balance of softening point, elongation and high-temperature storage stability is excellent.
• the hydrogenation rate can be determined by the method described in the examples described later.
• the block copolymer has a loss tangent peak top in the range of ⁇ 70 ° C. or more and 0 ° C. or less in the dynamic viscoelasticity spectrum, and the peak top value is 0.7 or more and 2.0 or less. Is preferred. There is a tendency that the performance balance of the softening point, elongation, and rutting resistance (G * / sin ⁇ ) of the asphalt composition is further improved.
• the range of the peak top of the loss tangent is more preferably ⁇ 50 ° C. or more and ⁇ 10 ° C. or less. More preferably, it is ⁇ 45 ° C. or higher and ⁇ 20 ° C. or lower.
• the peak top value is more preferably 0.8 or more and 1.6 or less, and further preferably 0.9 or more and 1.4 or less. More preferably, it is 1.0 or more and 1.3 or less.
• the tan ⁇ peak height and temperature can be determined by the method described in the examples described later.
• the tan ⁇ peak temperature controls, for example, the content ratio between the vinyl aromatic monomer unit and the conjugated diene monomer unit in the copolymer block (B), the microstructure of the conjugated diene compound, and the hydrogenation rate.
• the peak top of tan ⁇ can be adjusted in the range of ⁇ 70 ° C. or more and 0 ° C. or less.
• the ratio of vinyl aromatic monomer units in the copolymer block (B) is increased, the peak top of tan ⁇ tends to have a higher temperature, and when the ratio of vinyl aromatic monomer units is decreased, the peak of tan ⁇ is increased.
• the top tends to have on the low temperature side.
• the peak top value can be adjusted to 0.7 or more and 2.0 or less by controlling the temperature and the addition time or number of additions of each monomer in the polymerization of the copolymer block (B). Specifically, the conjugated diene monomer and the vinyl aromatic added at a constant rate within a range of 56 to 90 ° C. in the reactor, a pressure of 0.1 to 0.50 MPa in the reactor, and a constant rate.
• the monomer addition time is in the range of 10 to 60 minutes, or the number of additions is 3 or more.
• the peak top value is 0 when the temperature during the hydrogenation reaction is 80 ° C. or more and 120 ° C. or less. There is a tendency to approach 7 or more and 2.0 or less.
• the conjugated diene monomer unit includes a conjugated diene monomer unit (a) derived from a 1,2-bond and / or a 3,4-bond and a conjugated diene monomer derived from a 1,4-bond. It consists of a body unit (b).
• conjugated diene monomer unit (a) derived from 1,2-bond and / or 3,4-bond means that the conjugated diene compound is a 1,2-bond and / or 3,4-bond. Units per conjugated diene compound produced as a result of polymerization.
• conjugated diene monomer unit (b) derived from 1,4-bond is a unit per conjugated diene compound produced as a result of polymerization of a conjugated diene compound with 1,4-bond.
• the content of the conjugated diene monomer unit (a) relative to the total content of conjugated diene monomer units in the block copolymer is the softening point and elongation of the asphalt composition. From the viewpoint of the performance balance, it is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 45% by mass or less, and further preferably 20% by mass or more and 40% by mass or less.
• the content of the alkenyl monomer unit (a1) in which the conjugated diene monomer unit (a) is hydrogenated is The content of the alkenyl monomer unit (b1) in which the conjugated diene monomer unit (b) is hydrogenated is 10% by mass or more and 50% by mass or less, and is 0% by mass or more and 80% by mass or less.
• the sum of the contents of the conjugated diene monomer unit (a2) not hydrogenated after hydrogenation and the conjugated diene monomer unit (b2) not hydrogenated after hydrogenation is 0% by mass or more and 90% by mass or less. Preferably there is.
• the content of the alkenyl monomer unit (a1) is preferably 15% by mass or more and 45% by mass or less, more preferably 20% by mass or more and 40% by mass. It is below mass%.
• the content of the alkenyl monomer unit (b1) is preferably 10% by mass or more and 70% by mass or less, more preferably 15% by mass. It is 65 mass% or less, More preferably, it is 30 mass% or more and 65 mass% or less.
• the sum of the contents of the conjugated diene monomer unit (a2) and the conjugated diene monomer unit (b2) is preferably 0% by mass or more. It is 80 mass% or less, More preferably, it is 5 mass% or more and 70 mass% or less, More preferably, it is 10 mass% or more and 60 mass% or less.
• the content of the alkenyl monomer unit (a2) that has not been hydrogenated and the content of the alkenyl monomer unit (b2) that has not been hydrogenated can be determined by the methods described in the Examples described later.
• the content of the conjugated diene monomer unit (a) before hydrogenation in the block copolymer and the microstructure of the conjugated diene monomer unit (ratio of cis, trans to vinyl) can be determined by using a polar compound or the like described later. Can be adjusted.
• the block copolymer used in this embodiment is a hydroxyl group, an acid anhydride group, an epoxy group, an amino group in terms of high elongation of the asphalt composition, high elongation recovery, and high elongation at a low temperature such as 5 ° C. It preferably has at least one functional group selected from the group consisting of an amide group, a silanol group, and an alkoxysilane group. Among these, the block copolymer preferably has at least one functional group selected from the group consisting of an amino group and an amide group, and more preferably has an amino group.
• the block copolymer contains 2 mol or more of at least one functional group selected from the group consisting of an amino group and an amide group with respect to 1 mol of the molecule.
• the said functional group can be introduce
• the melt flow rate (MFR) of the block copolymer is preferably 0.05 or more and 10 or less, more preferably 0.05 or more and 8 or less, and further preferably 0.05 or more and 6 or less. It is.
• MFR melt flow rate
• the measurement of MFR can be calculated by a method according to JIS K7210 using a hydrogenated block copolymer and using a melt indexer (L247; manufactured by TECHNOLSEVEN CO., LTD).
• the test temperature is 230 ° C.
• the test load is 2.16 kgf
• the unit of the measured value is preferably measured under the L condition of g / 10 minutes.
• the weight average molecular weight (Mw) of the block copolymer is preferably 50,000 or more and 300,000 or less, more preferably 60000 or more and 280000 or less. Yes, more preferably from 70,000 to 260,000, and even more preferably from 70,000 to less than 200,000.
• the molecular weight distribution (Mw / Mn) of the block copolymer (ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) is Preferably, it is 2.0 or less, More preferably, it is 1.8 or less, More preferably, it is 1.5 or less.
• the weight average molecular weight and molecular weight distribution can be determined by the methods described in the examples described later.
• the block copolymer is hydrogenated, the weight average molecular weight and molecular weight distribution are almost equal to the weight average molecular weight and molecular weight distribution of the block copolymer before hydrogenation, so the block copolymer is hydrogenated.
• the weight average molecular weight and molecular weight distribution of the block copolymer before hydrogenation may be obtained as the weight average molecular weight and molecular weight distribution.
• any structure can be used as the structure of the block copolymer.
• a structure represented by a following formula is mentioned.
• each A independently represents a polymer block (A).
• Each B independently represents a copolymer block (B).
• Each n independently represents an integer of 1 or more. And preferably an integer of 1 to 5.
• Each m is independently an integer of 2 or more, preferably an integer of 2 to 11.
• Each X is independently a residue of a coupling agent or Represents the residue of a polyfunctional initiator.
• the block copolymer may be any mixture having the structure represented by the above formula.
• the ABA structure is preferable from the viewpoint of the balance of asphalt binder performance.
• the vinyl aromatic monomer units in the copolymer block (B) may be uniformly distributed, or may be distributed in a tapered shape, a staircase shape, a convex shape, or a concave shape.
• the “tapered structure” means a structure in which the content of vinyl aromatic monomer units gradually increases along the polymer chain in the copolymer block (B).
• the content of the vinyl aromatic monomer unit in the copolymer block (B) immediately after the start of polymerization of the copolymer block (B) is S1, during polymerization, for example, 1/2 of the introduced monomer is polymerized.
• copolymer block (B) a plurality of portions where the vinyl aromatic monomer units are uniformly distributed and / or portions where the vinyl aromatic monomer units are distributed in a tapered shape may exist. In the copolymer block (B), a plurality of segments having different vinyl aromatic monomer unit contents may be present.
• the block copolymer of the present embodiment can be produced, for example, by anion living polymerization using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent.
• the hydrocarbon solvent is not particularly limited.
• aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane; cyclohexane, cycloheptane, methylcycloheptane
• alicyclic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.
• the aliphatic hydrocarbon alkali metal compound which has anionic polymerization activity with respect to a conjugated diene and a vinyl aromatic compound an aromatic hydrocarbon alkali metal compound, an organic amino alkali metal compound, etc. Is mentioned.
• an alkali metal For example, lithium, sodium, potassium, etc. are mentioned.
• an organic alkali metal compound when used as a polymerization initiator to polymerize a conjugated diene compound and a vinyl aromatic compound, a vinyl bond (1,1) resulting from a conjugated diene monomer unit incorporated in the block copolymer
• a tertiary amine compound or an ether compound which is a polar compound, is added. Also good.
• tertiary amine compound is not particularly limited, for example, the formula R 1 R 2 R 3 N (provided that, R 1, R 2, R 3 are each independently a hydrocarbon group having 1 to 20 carbon atoms or a A hydrocarbon group having a tertiary amino group).
• the ether compound is not particularly limited, and examples thereof include a linear ether compound and a cyclic ether compound.
• Dialkyl ether compounds of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; Diethylene glycol And dialkyl ether compounds of diethylene glycol such as dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
• the cyclic ether compound is not particularly limited, and specific examples thereof include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl). ) Propane, alkyl ethers of furfuryl alcohol, and the like.
• the method for polymerizing the conjugated diene compound and the vinyl aromatic compound using the organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof.
• the polymerization temperature is usually 0 ° C. or higher and 180 ° C. or lower, preferably 30 ° C. or higher and 150 ° C. or lower.
• the time required for the polymerization varies depending on other conditions, but is usually within 48 hours, preferably 0.1 to 10 hours.
• the atmosphere of the polymerization system is preferably an inert gas atmosphere such as nitrogen gas.
• the polymerization pressure is not particularly limited as long as it is within a range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Care must be taken not to mix impurities (water, oxygen, carbon dioxide, etc.) that inactivate the catalyst and living polymer in the polymerization system.
• the coupling reaction can also be performed using a bifunctional or higher functional coupling agent when the polymerization is completed.
• a bifunctional or higher functional coupling agent there are no particular limitations on the bifunctional or higher functional coupling agent, and known coupling agents can be used.
• Dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane
• Acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, phthalates Etc.
• the trifunctional or higher polyfunctional coupling agent is not particularly limited.
• polyhydric alcohols having 3 or more valences polyvalent epoxy compounds such as epoxidized soybean oil and diglycidyl bisphenol A; formula R 4-n SiX n (Wherein each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a halogen atom, and n represents 3 or 4).
• a functional group can be added to the resulting block copolymer by using a compound having a functional group as an initiator, a monomer, a coupling agent, or a stopper.
• an initiator containing a nitrogen-containing group is preferable.
• Dioctylaminolithium, di-2-ethylhexylaminolithium, ethylbenzylaminolithium, (3- (dibutylamino) -propyl) lithium, Peridinolithium etc. are mentioned.
• Examples of the monomer containing a functional group include compounds containing a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group in the monomers used for the above-described polymerization.
• monomers containing a nitrogen-containing group are preferable, for example, N, N-dimethylvinylbenzylamine, N, N-diethylvinylbenzylamine, N, N-dipropylvinylbenzylamine, N, N-dibutylvinylbenzyl.
• Examples of the coupling agent and terminating agent containing a functional group include compounds containing a hydroxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, a silanol group, and an alkoxysilane group among the above-described coupling agents.
• a coupling agent containing a nitrogen-containing group or an oxygen-containing group is preferable.
• tetraglycidylmetaxylenediamine tetraglycidyl-1,3-bisaminomethylcyclohexane
• tetraglycidyl-p-phenylenediamine tetraglycidyldiaminodiphenylmethane
• Diglycidylaniline ⁇ -caprolactone
• ⁇ -glycidoxyethyltrimethoxysilane ⁇ -glycidoxypropyltrimethoxysilane
• ⁇ -glycidoxypropyltriphenoxysilane ⁇ -glycidoxypropylmethyldimethoxysilane
• ⁇ - Glycidoxypropyl diethylethoxysilane 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-d
• the production method in the case of hydrogenating the block copolymer is not particularly limited, and a known method can be used.
• the hydrogenation catalyst used when hydrogenating the block copolymer is not particularly limited, but conventionally known metals such as Ni, Pt, Pd, and Ru are carbon, silica, alumina, diatomaceous earth, and the like.
• a homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh, or Zr is used.
• hydrogenation catalysts described in JP-B-63-4841, JP-B-1-53851, and JP-B-2-9041 can be used.
• Preferred hydrogenation catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds.
• titanocene compound compounds described in JP-A-8-109219 can be used. Specifically, (substituted) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.
• organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
• the hydrogenation reaction of the block copolymer is usually performed within a temperature range of 0 to 200 ° C., preferably within a temperature range of 30 to 150 ° C.
• the pressure of hydrogen used in the hydrogenation reaction is usually from 0.1 MPa to 15 MPa, preferably from 0.2 MPa to 10 MPa, more preferably from 0.3 MPa to 5 MPa.
• the hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours.
• the hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.
• the catalyst residue can be removed if necessary, and the hydrogenated block copolymer can be separated from the solution.
• a method of separating the solvent for example, a method of adding a polar solvent that is a poor solvent for a hydrogenated block copolymer such as acetone or alcohol to the reaction solution after hydrogenation to precipitate and recover the block copolymer, Examples thereof include a method in which the reaction solution is poured into hot water with stirring and the solvent is removed by steam stripping, or a method in which the solvent is distilled off by directly heating the block copolymer solution.
• Stabilizers such as various phenol stabilizers, phosphorus stabilizers, sulfur stabilizers and amine stabilizers can be added to the block copolymer of this embodiment.
• the asphalt that can be used in the present embodiment is not particularly limited.
• asphalt that is obtained as a by-product during petroleum refining (petroleum asphalt), a natural product (natural asphalt), or these and petroleum products What mixed is mentioned. Its main component is called bitumen.
• bitumen Specifically, straight asphalt, semi-blown asphalt, blown asphalt, tar, pitch, cutback asphalt to which oil is added, asphalt emulsion and the like can be mentioned. These may be used alone or in combination of two or more.
• the asphalt of the present embodiment has a colloidal index ((saturated content (mass%) + asphaltene content (mass%) from the viewpoint of softening point and rutting resistance (G * / sin ⁇ ) of the asphalt composition. )) / (Resin content (mass%) + aromatic content (mass%)) is 0.30 to 0.54 and the saturated content is 11 mass% or less.
• the index is preferably 0.31 or more, more preferably 0.32 or more, still more preferably 0.36 or more, still more preferably 0.37 or more, and even more preferably 0.38.
• the colloidal index is 0.30 or more, the softening point and rutting resistance (G * / sin ⁇ ) are further improved.
• the index is preferably 0.53 or less, more preferably 0.52 or less, still more preferably 0.51 or less, even more preferably 0.50 or less, and the colloidal index is 0.54 or less. Therefore, workability (low melt viscosity) and elongation are further improved.
• the saturated content is preferably 10.0% by mass or less, more preferably 9.5% by mass or less, and further preferably 9.0% by mass or less.
• the saturated content is 11.0% by mass or less, the softening point and rutting resistance (G * / sin ⁇ ) tend to be further improved.
• the saturated content is preferably 4% by mass or more, more preferably 5% by mass or more, and further preferably 5.5% by mass or more.
• workability low melt viscosity
• elongation tend to be further improved.
• the asphaltene content is preferably 25% by mass or less, more preferably 24% by mass or less, and further preferably 23% by mass or less. When the asphaltene content is 26% by mass or less, workability (low melt viscosity) and elongation tend to be further improved.
• the asphaltene content is preferably 18% by mass or more, more preferably 18.5% by mass or more, and further preferably 19% by mass or more. When the asphaltene content is 16% by mass or more, the softening point and rutting resistance (G * / sin ⁇ ) tend to be further improved.
• the resin content is preferably 29% by mass or less, more preferably 28% by mass or less, and further preferably 27.5% by mass or less. When the resin content is 30% by mass or less, the elongation tends to be further improved.
• the resin content is preferably 19% by mass or more, more preferably 20% by mass or more, and further preferably 20.5% by mass or more. When the resin content is 18% by mass or more, the softening point, rutting resistance (G * / sin ⁇ ) and workability (low melt viscosity) tend to be further improved.
• the aromatic content is preferably 58% by mass or less, more preferably 56% by mass or less, and further preferably 54% by mass or less. When the aromatic content is 60% by mass or less, the softening point and rutting resistance (G * / sin ⁇ ) tend to be further improved.
• the aromatic content is preferably 38% by mass or more, more preferably 40% by mass or more, and further preferably 42% by mass or more. When the aromatic content is 35% by mass or more, workability (low melt viscosity) and elongation tend to be further improved.
• the colloidal index (Ci) of asphalt and the loss tangent peak temperature (Tg (° C.)) in the dynamic viscoelastic spectrum of the block copolymer preferably satisfy the following relationship. Thereby, there exists a tendency for a softening point and rutting resistance to improve more. Ci ⁇ 0.0127 ⁇ Tg + 0.94
• the peak top range of the loss tangent is preferably in the range of ⁇ 70 ° C. or more and 0 ° C. or less, more preferably ⁇ 50 ° C. or more and ⁇ 10 ° C. or less, and further preferably ⁇ 45 ° C. or more. It is ⁇ 20 ° C. or lower.
• the “saturated component” is an oil component of paraffin or naphthene having a molecular weight of 300 to 2,000
• the “asphalten component” is a condensed polycyclic aromatic having a layered structure having a molecular weight of 1,000 to 100,000.
• the “resin content” is a condensed polycyclic aromatic resin having a molecular weight of 500 to 50,000
• the “aromatic content” is an aromatic oil having a molecular weight of 500 to 2,000.
• Each of these components can be analyzed by a measuring method based on JPI-5S-70-10 of the Petroleum Institute Petroleum Testing Related Standards.
• the colloidal index and the saturation can be obtained by the method described in the examples described later.
• the penetration of asphalt is preferably more than 40 and 120 or less, preferably 50 or more and 100 or less, more preferably 60 or more and 120 or less.
• the penetration of asphalt can be measured by the method described in the examples. Further, the penetration of asphalt can be adjusted by controlling the temperature, time, degree of reduced pressure, etc., of petroleum refining conditions.
• the content of the block copolymer is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of asphalt from the viewpoint of the balance of melt viscosity, softening point and rutting resistance (G * / sin ⁇ ).
• they are 1 mass part or more and 18 mass parts or less, More preferably, they are 2 mass parts or more and 15 mass parts or less.
• it is preferably 0.5 parts by mass or more and 15 parts by mass or less, and a higher softening point and elongation can be obtained with respect to 100 parts by mass of asphalt.
• an asphalt waterproof sheet it is preferably 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of asphalt.
• Polymers other than the block copolymers described above From the viewpoint of high softening point, oil resistance or economy, a polymer other than the block copolymer described above may be included.
• examples of other polymers include, but are not limited to, natural rubber, polyisoprene rubber, polybutadiene rubber, styrene butadiene rubber, styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene-butylene-styrene copolymer.
• Olefin-based elastomers such as polymer (SBBS), styrene-ethylene-butylene-styrene copolymer (SEBS), ethylene propylene copolymer; ethylene-ethyl acrylate copolymer, chloroprene rubber, acrylic rubber, ethylene vinyl acetate copolymer Etc.
• a styrene-butadiene-styrene block copolymer is preferred from the viewpoint of the low viscosity of the asphalt composition and the high elongation at low temperature.
• the SBS preferably contains a styrene-butadiene diblock body. Examples of SBS include Kraton D1101 and D1184.
• the tackifier resin is not particularly limited, and examples thereof include rosin resins, hydrogenated rosin resins, terpene resins, coumarone resins, phenol resins, terpene-phenol resins, aromatic hydrocarbon resins. And known tackifying resins such as aliphatic hydrocarbon resins.
• the tackifier resin may be used alone or in combination of two or more. Specific examples of the tackifier resin include those described in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.).
• the workability and the elastic modulus are improved in the asphalt composition of the present embodiment.
• the content of the tackifier resin in the asphalt composition of the present embodiment is preferably in the range of 0 to 200 parts by mass, more preferably 10 to 100 parts by mass when the block copolymer described above is 100 parts by mass. Used in. By setting it as content of the said range, the improvement effect of workability and an elasticity modulus is acquired reliably.
• Softener A softener may be added to the asphalt composition of the present embodiment.
• a mineral oil softener or a synthetic resin softener can be used.
• mineral oil softeners include paraffinic oil, naphthenic oil, aromatic oil, and the like.
• Paraffinic hydrocarbons with 50% or more carbon atoms in all carbon atoms are called paraffinic oils, and naphthenic hydrocarbons with 30 to 45% carbon atoms are called naphthenic oils.
• aromatic oils having 35% or more carbon atoms of aromatic hydrocarbons are called aromatic oils.
• the synthetic resin softener is not particularly limited, and preferred examples include polybutene and low molecular weight polybutadiene.
• the softener paraffinic oil which is a softener for rubber is preferable. By containing the softening agent, the workability is improved in the asphalt composition of the present embodiment.
• the content of the softening agent in the asphalt composition of the present embodiment is the above-described block copolymer from the viewpoint of suppressing the bleed of the softening agent and ensuring practically sufficient mechanical strength in the asphalt composition of the present embodiment.
• it is 100 parts by mass, it is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and still more preferably 2 to 30 parts by mass.
• the antioxidant is not particularly limited.
• 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t- Butylphenyl) propionate 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,4-bis [(octylthio) Methyl] -o-cresol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6 -[1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl)] Hindered phenol antioxidants such
• Examples of the light stabilizer include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) benzotriazole, 2- ( Benzotriazole ultraviolet absorbers such as 2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole; benzophenone ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone; hindered amines System light stabilizers and the like.
• the content of the stabilizer in the asphalt composition of the present embodiment is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass with respect to 100 parts by mass of the block copolymer.
• the range of ⁇ 3 parts by mass is more preferred, and the range of 0.2 ⁇ 2 parts by mass is more preferred.
• additives conventionally used in asphalt compositions can be added to the asphalt composition of the present embodiment as needed.
• fillers and reinforcing agents such as silica, talc, calcium carbonate, mineral powder, glass fiber, mineral aggregates, pigments such as bengara, titanium dioxide, paraffin wax, microcrystalline wax, low molecular weight polyethylene wax, etc.
• Waxes or foaming agents such as azodicarbonamide, atactic polypropylene, polyolefin-based thermoplastic resins such as ethylene-ethyl acrylate copolymer, low molecular weight vinyl aromatic thermoplastic resins, natural rubber, polyisoprene rubber, polybutadiene rubber, Styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, polypentenamer rubber, styrene-butadiene block copolymers other than the present invention, and styrene-isoprene block copolymers Coalescence, hydrogenated styrene - butadiene block copolymer, hydrogenated styrene - include synthetic rubbers such as isoprene block copolymer.
• the content of the additive in the asphalt composition of the present embodiment is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass with respect to 100 parts by mass of the block copolymer.
• the range of 0 to 30 parts by mass is more preferable, and the range of 1 to 20 parts by mass is even more preferable.
• Rubber vulcanizing agent and crosslinking agent examples include sulfur, sulfur compounds, inorganic vulcanizing agents other than sulfur, oximes, nitroso compounds, polyamines, organic peroxides, and resin vulcanizing agents.
• Plasticizer for example, phthalic acid derivative, tetrahydrophthalic acid derivative, adipic acid derivative, azelaic acid derivative, sebacic acid derivative, dodecane-2-acid derivative, maleic acid derivative, fumaric acid derivative, trimellitic acid derivative, pyromellitic acid derivative,
• Examples include citric acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, sulfonic acid derivatives, phosphoric acid derivatives, glutaric acid derivatives, glycol derivatives, glycerin derivatives, paraffin derivatives, and epoxy derivatives.
• Nucleating agent fatty acid metal salt type, sorbitol type, phosphate metal salt type.
• the content of the other components in the asphalt composition of the present embodiment is preferably 0 to 10 parts by mass with respect to 100 parts by mass of the block copolymer described above in the asphalt composition of the present embodiment.
• the range of 0 to 5 parts by mass is more preferred, the range of 0 to 3 parts by mass is more preferred, and the range of 0.2 to 2 parts by mass is even more preferred.
• the pavement form using the asphalt composition is not particularly limited. Pavement and thin layer pavement are listed.
• the content of the block copolymer in the asphalt composition is preferably 3 to 5.5% by mass with respect to 100% by mass of asphalt.
• the composition of the asphalt composition that can be used for dense-graded pavement is preferably 40 to 55% by mass of coarse aggregate and 100% by mass (excluding asphalt) of each aggregate and filler. Aggregate is 40 to 50% by mass, filler is 3 to 5% by mass, and asphalt is 5 to 7% by mass.
• the content of the block copolymer in the asphalt composition is preferably 5 to 10% by mass with respect to 100% by mass of asphalt.
• the composition of the asphalt composition that can be used for drainage pavement is preferably 60 to 85% by weight of coarse aggregate and 100% by weight (excluding asphalt) of each aggregate and filler. Aggregate is 5 to 20% by mass, filler is 3 to 5% by mass, and asphalt is 4 to 6% by mass.
• the content of the block copolymer in the asphalt composition is preferably 0.5 to 6% by mass with respect to 100% by mass of asphalt.
• the composition of the asphalt composition that can be used for water-permeable pavement is preferably 60 to 85% by weight of coarse aggregate and 100% by weight (excluding asphalt) of each aggregate and filler. Aggregate is 5 to 20% by mass, filler is 3 to 5% by mass, and asphalt is 4 to 6% by mass.
• the content of the block copolymer in the asphalt composition is preferably 5 to 12% by mass with respect to 100% by mass of asphalt.
• the composition of the asphalt composition that can be used for dense grain gap pavement is preferably 50 to 60% by mass of coarse aggregate with respect to the total amount of each aggregate and filler of 100% by mass (excluding asphalt).
• the fine aggregate is 30 to 40% by mass
• the filler is 3 to 6% by mass
• the asphalt is 4.5 to 6% by mass.
• Crushed stone mastic asphalt pavement is mainly required to improve wearability, water impermeability, stress relaxation, flow resistance, and noise resistance.
• the content of the block copolymer in the asphalt composition is preferably 4 to 10% by mass with respect to 100% by mass of asphalt.
• the composition of the asphalt composition that can be used in the crushed stone mastic asphalt pavement is as follows. The total amount of each aggregate and filler is 100% by mass (excluding asphalt), and the coarse aggregate is 55 to 70% by mass. 15 to 30% by mass, filler 5 to 10% by mass, and asphalt 5.5 to 8% by mass.
• the content of the block copolymer in the asphalt composition is preferably 4 to 10% by mass with respect to 100% by mass of asphalt.
• the composition of the asphalt composition that can be used for semi-flexible pavement is preferably 60 to 85% by mass of coarse aggregate with respect to the total amount of each aggregate and filler of 100% by mass (excluding asphalt).
• the fine aggregate is 5 to 20% by mass
• the filler is 3 to 5% by mass
• the asphalt is 4 to 6% by mass
• the void is preferably filled with cement-based mortar with a porosity of about 15 to 20%.
• the content of the block copolymer in the asphalt composition is preferably 4 to 10% by mass with respect to 100% by mass of asphalt.
• the composition of the asphalt composition that can be used for water-retaining pavement is 60 to 85% by weight of coarse aggregate and 5% of fine aggregate with respect to the total amount of aggregate and filler of 100% by weight (excluding asphalt). It is preferably 20 to 20% by mass, filler 3 to 5% by mass, and asphalt 4 to 6% by mass. Further, it is preferable to fill the voids with a water retention material such as cement or gypsum with a porosity of about 15 to 20%.
• the content of the block copolymer in the asphalt composition is preferably 4 to 8% by mass with respect to 100% by mass of asphalt.
• the composition of the asphalt composition that can be used for the thin-layer pavement is preferably an aggregate (5 to 2.5 mm) 60 with respect to a total amount of each aggregate and filler of 100% by mass (excluding asphalt). 85 mass%, fine aggregate (2.5 mm or less) 5-20 mass%, filler 3-5 mass%, asphalt 4-6.5 mass%.
• the manufacturing method of the asphalt composition of this embodiment is not specifically limited, It can manufacture by the method of heat-melt-kneading each component with a well-known mixer, a hot-melting pot, a kneader, etc., and mixing uniformly.
• asphalt is immersed in a hot melting kettle at 160 ° C to 200 ° C (usually around 180 ° C), completely melted, and stirred with a stirrer such as a homomixer while adding a block copolymer and other predetermined additions.
• An asphalt composition can be produced by adding an agent, then increasing the stirring speed and kneading.
• the normal stirring speed may be appropriately selected depending on the apparatus used, but is usually 100 rpm or more and 8,000 rpm or less, and the stirring time is preferably 30 minutes to 6 hours, more preferably 1 hour to 3 hours. .
• Measurement condition Measuring equipment: JNM-LA400 (manufactured by JEOL) Solvent: Deuterated chloroform Measurement sample: Sample taken before and after hydrogenation of block copolymer Sample concentration: 50 mg / mL Observation frequency: 400 MHz Chemical shift criteria: TMS (tetramethylsilane) Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 ° Measurement temperature: 26 ° C
• the content of the alkenyl monomer unit (a1) in which the conjugated diene monomer unit (a) is hydrogenated, the conjugated diene monomer unit (b) Content of alkenyl monomer unit (b1) hydrogenated, content of alkenyl monomer unit (a2) not hydrogenated, content of alkenyl monomer unit (b2) not hydrogenated was calculated.
• (III-2) Softening point The softening point of the asphalt composition was measured according to JIS-K2207. When the sample is filled in the specified ring, supported horizontally in the glycerin liquid, a 3.5 g sphere is placed in the center of the sample, and the liquid temperature is increased at a rate of 5 ° C./min. Measured the temperature when touching the bottom plate of the ring base. If the measured value (° C) of the softening point is 75 or more, it is a practically excellent performance, if it is 82 or more, it is a practically sufficient performance, and if it is 120 or more, it is also practically excellent as an asphalt tarpaulin application. If the performance was 130 or more, it was judged that the performance was practically sufficient.
• G * / sin ⁇ was evaluated as an index of rudder digging ability.
• G * / sin ⁇ was determined by measuring a viscoelastic spectrum using a viscoelasticity measuring / analyzing apparatus ARES (trade name, manufactured by T.A. Insulation Japan Co., Ltd.). Measurement materials were set in a torsion type geometry, and G * (complex elastic modulus) and sin ⁇ were measured at a strain of 0.5%, a measurement frequency of 1 Hz, and a parallel plate diameter of 7.9 mm.
• the measured value (Pa) of G * / sin ⁇ was 750 or more, it was judged that the performance was practically excellent, and when it was 900 or more, the performance was practically sufficient.
• n-butyllithium was 0.058% by mass relative to the mass of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor),
• TMEDA N, N, N ′, N′-tetramethylethylenediamine
• n-butyllithium added is 0.037% by mass, 10 parts by mass of styrene supplied in the first stage, 70 parts by mass of butadiene supplied in the second stage, 10 parts by mass of styrene, and the addition time of butadiene was polymerized by the same method as for polymer 1 except that the styrene supplied to the third stage was changed to 10 parts by mass for 15 minutes.
• n-butyllithium added is 0.063% by mass, 17.5 parts by mass of styrene supplied in the first stage, 50 parts by mass of butadiene supplied in the second stage, 15 parts by mass of styrene, 3 parts Polymerization was performed in the same manner as for Polymer 1 except that the amount of styrene supplied to the eye was changed to 17.5 parts by mass.
• n-butyllithium 0.045% by mass
• styrene supplied in the first stage is 7.5 parts by mass
• butadiene supplied in the second stage is 62 parts by mass
• the addition time of butadiene is 20 minutes.
• Polymerization was performed in the same manner as for Polymer 1 except that the amount of styrene supplied to the third stage was changed to 7.5 parts by mass.
• n-butyllithium 0.077% by mass, 12.5 parts by mass of styrene supplied to the first stage, 45 parts by mass of butadiene to be supplied to the second stage, 30 parts by mass of styrene, Polymer 1 and Polymer 1 except that the addition time is 45 minutes, the styrene supplied in the third stage is changed to 12.5 parts by mass, the reactor internal temperature is adjusted to 85 ° C., and the reactor internal pressure is adjusted to 0.42 MPa. Polymerization was carried out in the same manner.
• n-butyllithium added is 0.056% by mass, 10 parts by mass of styrene supplied in the first stage, 57 parts by mass of butadiene supplied in the second stage, and the addition time of butadiene for 25 minutes, 3 stages Polymerization was performed in the same manner as for Polymer 1 except that the amount of styrene supplied to the eye was changed to 10 parts by mass.
• n-butyllithium added is 0.070% by mass, 15.5 parts by mass of styrene supplied in the first stage, 30 parts by mass of butadiene supplied in the second stage, 39 parts by mass of styrene, Polymerization was carried out in the same manner as for Polymer 1 except that the addition time was 55 minutes and the styrene supplied to the third stage was changed to 15.5 parts by mass.
• n-butyllithium added is 0.042% by mass, 6 parts by mass of styrene supplied in the first stage, 85 parts by mass of butadiene supplied in the second stage, 3 parts by mass of styrene, and the addition time of butadiene was carried out in the same manner as for polymer 1 except that the amount of styrene supplied to the third stage was changed to 6 parts by mass for 10 minutes.
• n-butyllithium added is 0.048% by mass, 4 parts by mass of styrene supplied in the first stage, 78 parts by mass of butadiene supplied in the second stage, 14 parts by mass of styrene, and the addition time of butadiene was carried out in the same manner as for polymer 1 except that the amount of styrene supplied to the third stage was changed to 4 parts by mass for 10 minutes.
• n-butyllithium added is 0.062% by mass, 23 parts by mass of styrene supplied to the first stage, 50 parts by mass of butadiene to be supplied to the second stage, 5 parts by mass of styrene, and the third stage. Polymerization was carried out in the same manner as in Polymer 1 except that the supplied styrene was changed to 22 parts by mass.
• the obtained block copolymer was subjected to a hydrogenation reaction in the same manner as the polymer 1 to obtain a hydrogenated block copolymer (hereinafter referred to as polymer 10).
• the hydrogenation rate was 84%.
• n-butyllithium added is 0.057% by mass, 15 parts by mass of styrene supplied in the first stage, 51 parts by mass of butadiene supplied in the second stage, 19 parts by mass of styrene, and the addition time of butadiene
• the polymerization was carried out in the same manner as in Polymer 1 except that the temperature inside the reactor was adjusted to 75 ° C. for 35 minutes, and the styrene supplied to the third stage was changed to 15 parts by mass.
• n-butyllithium added is 0.065% by mass, 10 parts by mass of styrene supplied in the first stage, 50 parts by mass of butadiene supplied in the second stage, 30 parts by mass of styrene, and the addition time of butadiene For 40 minutes in the same manner as Polymer 1 except that the styrene supplied to the third stage is changed to 10 parts by mass, the reactor internal temperature is adjusted to 95 ° C., and the reactor internal pressure is adjusted to 0.52 MPa. Polymerization was performed.
• n-butyllithium 0.062% by mass, 20 parts by mass of styrene supplied to the first stage, 61 parts by mass of butadiene to be supplied to the second stage, and no addition of styrene. Polymerization was carried out in the same manner as for Polymer 1 except that the supplied styrene was changed to 19 parts by mass.
• the polymer 15 was obtained without performing a hydrogenation reaction.
• the hydrogenation rate was 0%.
• n-butyllithium added is 0.057% by mass, 10 parts by mass of styrene supplied in the first stage, 57 parts by mass of butadiene supplied in the second stage, and the addition time of butadiene for 25 minutes, 3 stages
• 0.9 mol of N, N′-dimethylpropyleneurea was added to 1 mol of n-butyllithium added before the first step. Polymerization was carried out in the same manner.
• TMEDA was added in an amount of 0.05 mol per mol of n-butyllithium, the amount of n-butyllithium added was 0.105 parts by mass, and 15 parts by mass of styrene supplied to the first stage was added to the second stage.
• Polymerization was carried out in the same manner as in Polymer 1 except that 70 parts by mass of butadiene to be supplied and 15 parts by mass of styrene to be supplied in the third stage were added without adding dimethyldichlorosilane.
• the hydrogenation reaction was not performed, and polymer 18 was obtained.
• the hydrogenation rate was 0%.
• Example 1 400g colloidal index (Ci value) is 0.36, saturation is 5.4% by mass, aromatic content is 52.78% by mass, resin content is 20.69% by mass, asphaltene content is 21.13% by mass) Of straight asphalt (manufactured by Keisei Oil (Korea)) was placed in a 750 cc container, and the container was immersed in an oil bath at 180 ° C. to completely dissolve the straight asphalt.
• Examples 2 to 9, Comparative Examples 1 to 8 As shown in Table 2 below, an asphalt composition was obtained by the same kneading method as in Example 1, using a predetermined polymer, making the ratio of each block copolymer and asphalt the same as in Example 1. Table 2 shows the physical properties of the obtained asphalt compositions. As the asphalt having a colloidal index (Ci value) of 0.36, Storus 60-80 manufactured by Kyodo Seiyaku of Korea was used.
• Example 10 As shown in Table 2 below, an asphalt composition was obtained by the same kneading method as in Example 1 except that 8 g of polymer 6 and 8 g of polymer 18 were added. Table 2 shows the physical properties of the obtained asphalt compositions.
• Example 11 As shown in Table 2 below, an asphalt composition was obtained by the same kneading method as in Example 1 except that 12 g of polymer 17 and 4 g of EVA polymer were added. Table 2 shows the physical properties of the obtained asphalt compositions.
• Example 12 As shown in Table 2 below, after adding 14 g of polymer 6, 0.1% by mass of sulfur is added to the asphalt composition, stirred for 120 minutes after the addition, and cured at 160 ° C. for 12 hours to obtain an asphalt composition.
• An asphalt composition was prepared in the same manner as in Example 1 except that. Table 2 shows the physical properties of the obtained asphalt compositions.
• Example 13 As shown in Table 2 below, asphalt was obtained in the same manner as in Example 12 except that 8 g of polymer 6 and 8 g of polymer 18 were added, and 0.2% by mass of polyphosphoric acid (manufactured by Kishida Chemical Co., Ltd.) was added to the asphalt composition. A composition was prepared. Table 2 shows the physical properties of the obtained asphalt compositions.
• Examples 14 to 16, Comparative Examples 9 to 11 As shown in Table 3 below, an asphalt composition was obtained by the same kneading method as in Example 1 using a predetermined polymer and according to the ratio of each block copolymer to asphalt. Table 3 shows the physical properties of the obtained asphalt compositions.
• the colloidal index (Ci value) is 0.5 (saturated content: 10.6% by mass, aromatic content: 43.1% by mass, resin content: 23.6% by mass, asphaltene content: 22.6% by mass)
• Stors 70-80 manufactured by Petro Chem was used as the 55th asphalt.
• the asphalt having a colloidal index (Ci value) of 0.36 was the same as that described above.
• Examples 17 to 20 As shown in Table 3 below, the asphalt of Example 17 and Example 20 has a colloidal index (Ci value) of 0.41 (saturation: 7.4% by mass, aromatic content: 47.8% by mass, Asphalt having a resin content of 23.3% by mass and an asphaltene content of 21.5% by mass is a Korean store 60-60, and the asphalts of Examples 18 and 19 have a colloidal index (Ci value) of 0.
• the asphalt composition of the present invention has a high softening point, high elongation, low melt viscosity, and excellent rutting resistance and high-temperature storage stability. Further, it was found that the asphalt compositions of Examples 1 to 13 were good for road paving, and the asphalt compositions of Examples 14 to 16 were good for asphalt waterproof sheets, and had excellent processability. .
• the asphalt composition of the present invention has industrial applicability as asphalt for road pavement, asphalt waterproof sheet and the like, and can be suitably used particularly in the field of road pavement.

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